CN113801331B - 一种水性超支化聚酯基环氧固化剂及其制备方法 - Google Patents
一种水性超支化聚酯基环氧固化剂及其制备方法 Download PDFInfo
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Abstract
本发明属于水性环氧树脂固化剂领域,公开了一种水性超支化聚酯基环氧固化剂的制备方法,包括如下步骤:将固态端羧基超支化聚酯树脂在丙二醇甲醚醋酸酯助溶剂中加热至溶解;再加入单端环氧聚二甲基硅氧烷和催化剂,混合均匀后,在100℃~130℃条件下,反应4~5h;将上述反应物冷却后,再加入有机胺中和,最后加水高速搅拌,得到水性超支化聚酯基环氧固化剂水分散液。本发明整个工艺流程简单,制备的水性超支化聚酯基环氧固化剂赋予水性环氧涂层优异的韧性、低表面能和优异的耐腐蚀性能。
Description
技术领域
本发明属于水性环氧树脂固化剂技术领域,具体涉及一种水性超支化聚酯基环氧固化剂及其制备方法。
背景技术
环氧树脂涂料具有优良的物理机械性能、高附着力、耐化学性以及灵活的使用工艺等优点广泛应用于建筑、化工、机械和电子封装等领域。但其产品主要以溶剂型为主,在其制造、施工、固化成膜过程中释放大量VOCs,对人类健康和生态环境构成严重的危害。因此,以水为溶剂或分散介质的水性环氧涂料逐渐受到人们的青睐。由于环氧树脂为热固性树脂,自身单独成膜时不具有使用价值,只有当加入环氧固化剂时,才能形成三维网状交联结构,显示出其优异的性能。
目前,市售水性环氧固化剂一般是在环氧-多胺加成物中引入亲水链段制得。例如CN110511356A公开了一种环氧-多胺加成物类的水性环氧树脂固化剂,其采用耐水性优异和韧性良好的环氧苯基硅油改性环氧树脂改善水性环氧涂膜高吸水率和易脆等问题;CN113214455A公开了一种增韧型水性环氧固化剂,通过引入增韧性环氧树脂和亲水链段烷基聚乙二醇单缩水甘油醚改性多元胺来制得一种水分散性良好、韧性优良且与水性环氧树脂相容性的固化剂。但是,此类固化剂往往会引入大量亲水性基团,所制涂膜具有较高的表面能,导致其耐水性和耐腐蚀性能降低。
发明内容
本发明旨在提供一种低表面能水性超支化聚酯基环氧固化剂及其制备方法,解决现有固化剂固化水性环氧树脂所得涂膜质脆、耐水性差、长期防腐蚀性能不足等问题。
本发明采用的技术方案如下:
一种水性超支化聚酯基环氧固化剂的制备方法,包括如下步骤:
将固态端羧基超支化聚酯树脂在丙二醇甲醚醋酸酯助溶剂中加热至溶解;再加入单端环氧聚二甲基硅氧烷和催化剂,混合均匀后,在100℃~130℃条件下,反应4~5h;将上述反应物冷却后,再加入有机胺中和,最后加水高速搅拌,得到无色透明的水性超支化聚酯基环氧固化剂水分散液。
优选地,所述端羧基超支化聚酯树脂的羧基数n=6~48,分子量1k~12k,其简化结构式如下:
优选地,所述端羧基超支化聚酯树脂的羧基数n=6-24。
优选地,所述单端环氧聚二甲基硅氧烷,其环氧值为0.075~0.0055,其简化结构如下:
优选地,所述单端环氧聚二甲基硅氧烷的环氧值为0.04~0.0125。
优选地,所述催化剂为三苯基膦、2-苯基咪唑、三氟化硼乙醚、四丁基溴化铵中的一种或两种以上。
优选地,所述有机胺中和剂为二乙胺、三乙胺、乙醇胺、二乙醇胺中的一种或两种以上;
优选地,所述单端环氧聚二甲基硅氧烷与端羧基超支化聚酯树脂的投料质量比为0.5%~3%;所述有机胺与端羧基超支化聚酯树脂的投料质量比为10%~25%。
优选地,所述高速搅拌的条件为6000~7500rpm;所述最终水性超支化聚酯基环氧固化剂的固含量为50%~60%。
本发明的原理是特别选择端羧基超支化聚酯作为环氧树脂固化剂,提高环氧树脂的韧性和耐水性。同时,选择单端环氧聚二甲基硅氧烷改性超支化聚酯树脂,可赋予涂膜高韧性和低表面能。此外,采用有机胺中和超支化聚酯的端羧基使其水分散,避免了常规多元胺固化剂中引入亲水链段而导致涂膜耐水性下降的问题。整个工艺流程简单,制备的水性超支化聚酯基环氧固化剂赋予水性环氧涂膜高韧性、低表面能和优异的耐腐蚀性能。
本发明的制备方法及所得到的产物具有如下优点及有益效果:
(1)水性超支化环氧固化剂合成工艺简单、稳定性好,与水性环氧树脂适配性高。
(2)低表面能的无氟水性环氧涂层体系环保、安全、并具有性价比优势,原料均使用工业化市场化的原料。
(3)涂层可适用于金属、玻璃、塑料、木器、陶瓷等多种基材,具有良好的附着力。
(4)涂层具有高硬度的同时兼具良好的韧性。
(5)涂层具有优异的耐水性和耐腐蚀性能。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
本发明端羧基超支化聚酯树脂选自武汉超支化树脂科技有限公司Hyper-C102。
单端环氧聚二甲基硅氧烷选自安徽艾约塔硅油有限公司。
实施例1
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。再加入0.13g单端环氧聚二甲基硅氧烷(环氧值n=0.025),再加入三氟化硼乙醚,搅拌均匀,升温至110℃,保温反应5h。冷却至室温,加入4g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
实施例2
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。再加入0.26g单端环氧聚二甲基硅氧烷(环氧值n=0.025),搅拌均匀,再加入三氟化硼乙醚,然后升温至110℃,保温反应4~5h。冷却至室温,加入4g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
实施例3
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。再加入0.52g单端环氧聚二甲基硅氧烷(环氧值n=0.025),搅拌均匀,再加入三氟化硼乙醚,然后升温至110℃,保温反应4~5h。冷却至室温,加入4g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
实施例4
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。再加入0.72g单端环氧聚二甲基硅氧烷(环氧值n=0.025),搅拌均匀,再加入三氟化硼乙醚,然后升温至110℃,保温反应4~5h。冷却至室温,加入4g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
实施例5
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。再加入0.52g单端环氧聚二甲基硅氧烷(环氧值n=0.04),搅拌均匀,再加入三氟化硼乙醚,然后升温至110℃,保温反应4~5h。冷却至室温,加入4g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
实施例6
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。再加入0.52g单端环氧聚二甲基硅氧烷(环氧值n=0.0125),搅拌均匀,再加入三氟化硼乙醚,然后升温至110℃,保温反应4~5h。冷却至室温,加入4g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
对比例1
将26g端羧基超支化树脂加入到装有搅拌器和冷凝器的250mL三口烧瓶中,加入6g丙二醇甲醚醋酸酯,油浴升温至90℃,使树脂溶解。冷却至室温,加入5g三乙胺中和反应30min,再加入去离子水高速(6000~7500rpm)分散30min,得到固含量55%的无色透明水分散液。
对比例2
市售环氧-多胺类水性环氧固化剂。
将上述实施例1-6、对比例1-2得到的水性环氧固化剂与市售水性环氧树脂(佛山市高明同德树脂有限公司3EE104W)按照理论化学反应计量数混合均匀,即水性固化剂中羧基/胺氢的摩尔数与环氧基团的摩尔数之比为0.9:1。然后,在钢板上涂膜,室温放置1~2h后,120℃~150℃固化2~3h,不同固化剂所对应的涂膜性能测试结果如表1所示。
表1:各实施例和对比例固化后所得涂膜性能测试结果
上述测试结果参照以下测试方法或标准:
划格法测定附着力,GB/T 9286-1998;
测定漆膜铅笔硬度,GB/T 6739-1996;
测定漆膜柔韧性,GB/T 1731-1993;
测定耐水性,GB/1733-1993;
耐盐水的测试方法为:将涂膜钢板置于3.5wt%氯化钠溶液中浸泡30d,观察涂膜表面有无起泡和发白,铁基材表面有无腐蚀发生及腐蚀严重程度;
水接触角测试:采用上海中晨JC2000D接触角测量仪。
由对比结果可看出,本发明采用的一种水性超支化聚酯基环氧固化剂及其制备方法所制备的水性环氧涂层,其韧性、耐水性和耐腐蚀性能都有显著的提升。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种水性超支化聚酯基环氧固化剂的制备方法,其特征在于,包括如下步骤:
将固态端羧基超支化聚酯树脂在丙二醇甲醚醋酸酯助溶剂中加热至溶解;再加入单端环氧聚二甲基硅氧烷和催化剂,混合均匀后,在100℃~130℃条件下,反应4~5h;将上述反应物冷却后,再加入有机胺中和,最后加水高速搅拌,得到水性超支化聚酯基环氧固化剂水分散液;
所述端羧基超支化聚酯树脂的羧基数n=6~48,分子量1k~12k;
所述单端环氧聚二甲基硅氧烷,其环氧值为0.0055~0.075,其结构如下:
所述单端环氧聚二甲基硅氧烷与端羧基超支化聚酯树脂的投料质量比为0.5%~3%;所述有机胺与端羧基超支化聚酯树脂的投料质量比为10%~25%。
2.根据权利要求1所述的制备方法,其特征在于,所述端羧基超支化聚酯树脂的羧基数n=6-24。
3.根据权利要求1所述的制备方法,其特征在于,所述单端环氧聚二甲基硅氧烷的环氧值为0.0125~0.04。
4.根据权利要求1或2或3所述的制备方法,其特征在于,所述催化剂为三苯基膦、2-苯基咪唑、三氟化硼乙醚、四丁基溴化铵中的一种或两种以上。
5.根据权利要求4所述的制备方法,其特征在于,所述有机胺中和剂为二乙胺、三乙胺、乙醇胺、二乙醇胺中的一种或两种以上;
6.根据权利要求1或2或3所述的制备方法,其特征在于,所述高速搅拌的条件为6000~7500rpm;所述水性超支化聚酯基环氧固化剂的固含量为50%~60%。
7.权利要求1~6任意一项所述方法制得的水性超支化聚酯基环氧固化剂。
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